Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B11/00—Diaryl- or thriarylmethane dyes
  • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
  • C09B11/10—Amino derivatives of triarylmethanes
  • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/26—Thermosensitive paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/333—Colour developing components therefor, e.g. acidic compounds
  • B41M5/3333—Non-macromolecular compounds
  • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/333—Colour developing components therefor, e.g. acidic compounds
  • B41M5/3333—Non-macromolecular compounds
  • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
  • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides

Definitions

• the present invention relates to a heat distribution display body and a temperature distribution confirmation method.
• a heat pressing process in which a heat sensitive sheet is stacked in an object to be processed or its material, supplied between opposing hot press surfaces, and hot pressing is performed
• Proposed is a temperature measurement method having a concentration measurement process for measuring the concentration of a measurement location in the heat-sensitive sheet after the heat press and a temperature calculation process for calculating the heating temperature of the hot press based on the measured concentration (See, for example, JP-A-2004-117145).
• the pseudo surface temperature sensor measures each point in principle even if a large number of measurement locations are dispersed. Therefore, when measuring the temperature of a wide hot press surface, important measurement points are often not included in the measurement points. In addition, the estimated temperature value obtained by interpolation may not be accurate enough.
• thermosensitive recording materials and thermal sheets as described above have high color sensitivity, the temperature range for sensing the heat of the object is narrow, and the color density increases rapidly with a small temperature difference. It was difficult to confirm the heat distribution.
• the present invention is capable of displaying a heat distribution with a large temperature difference (for example, 30 ° C. or more), and has a heat distribution display body excellent in raw storage stability of the heat distribution display body, and the same.
• An object is to provide a temperature distribution confirmation method.
• the electron-accepting compound B content ratio (A: B) is 95: 5 to 50:50 on a mass basis, and the electron-accepting compound represented by the general formula (1) in the total electron-accepting compound It is a heat distribution display body which has a heat distribution display layer whose content ratio of the property compound A is 40 mass% or more.
• R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, halogen atom, amino group, carboxy group, carbamoyl group, hydroxy group, alkylsulfonyl group, alkyl group. Or an aryl group, and two adjacent R 1 to R 4 may be bonded to form a ring.
• M represents an n-valent metal atom, and n represents an integer of 1 to 3.
• R 1 to R 10 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or Represents a phenylsulfonyl group, and at least one of R 1 to R 10 is a hydroxy group.
• X represents —S—, —SO 2 —, —SO 2 NH—, or —OCH 2 CH 2 O—.
• DA represents the optical density of the color-developing portion that has developed color by heating the heat distribution display layer to the temperature TA
• DB represents the heat distribution display layer heated to the temperature TB.
• the color density represents the optical density of the developed color part
• DC represents the optical density of the color developed part that developed color by heating the heat distribution display layer to the temperature TC.
• ⁇ 4> The heat distribution display according to ⁇ 3>, wherein a temperature difference (TB ⁇ TA) between the TA and the TB is 30 ° C. or more.
• ⁇ 5> The heat distribution display body according to ⁇ 3> or ⁇ 4>, in which the TA, the TB, the DA, and the DB satisfy the following formula (3).
• ⁇ 7> A temperature distribution confirmation method using the heat distribution display body according to any one of ⁇ 1> to ⁇ 6>.
• the present invention it is possible to display a heat distribution of a large temperature difference (for example, 30 ° C. or more), and a heat distribution display body excellent in raw preservation of the heat distribution display body, and a temperature distribution confirmation using the heat distribution display body A method can be provided.
• a large temperature difference for example, 30 ° C. or more
• the present invention provides an organic polymer composite containing an electron donating dye precursor and a polymer on a support, and an electron accepting property represented by the following general formula (1) for coloring the electron donating dye precursor. It contains at least the compound A and an electron-accepting compound B represented by the following general formula (2) and a binder, and the electron-accepting compound A represented by the general formula (1) and the general formula (2)
• the content ratio (A: B) of the electron-accepting compound B represented is 95: 5 to 50:50 on a mass basis, and is represented by the general formula (1) in the total electron-accepting compound. It has the heat distribution display layer whose content rate of the electron-accepting compound A is 40 mass% or more.
• R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, halogen atom, amino group, carboxy group, carbamoyl group, hydroxy group, alkylsulfonyl group, alkyl group. Or an aryl group, and two adjacent R 1 to R 4 may be bonded to form a ring.
• M represents an n-valent metal atom, and n represents an integer of 1 to 3.
• R 1 to R 10 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or Represents a phenylsulfonyl group, and at least one of R 1 to R 10 is a hydroxy group.
• X represents —S—, —SO 2 —, —SO 2 NH—, or —OCH 2 CH 2 O—.
• the heat distribution display of the present invention may have other layers such as a protective layer and a back layer in addition to the heat distribution display layer as long as the effects of the present invention are not impaired.
• the heat distribution display layer in the heat distribution display of the present invention comprises an organic polymer complex containing an electron donating dye precursor and a polymer, a specific electron accepting compound that develops color of the electron donating dye precursor, Containing a binder.
• the specific electron-accepting compound includes at least two of the electron-accepting compound represented by the general formula (1) and the electron-accepting compound represented by the general formula (2).
• the content ratio of A and B is 95: 5 to 50:50
• the content ratio of the electron-accepting compound A represented by the general formula (1) in the total electron-accepting compound is 40% by mass or more.
• the electron-donating dye precursor and the electron-accepting compound contained in the heat distribution display layer in the present invention both have excellent transparency when not treated, but are applied with heat energy from outside such as heating and heating.
• the two react to form a dye by giving and receiving electrons from each other to form a color.
• one heat distribution display layer in the present invention may be provided, or two or more layers may be provided.
• the essential components contained in the heat distribution display layer and other components that may be optionally contained will be described.
• the heat distribution display layer in the present invention contains at least two kinds of an electron accepting compound represented by the following general formula (1) and an electron accepting compound represented by the following general formula (2).
• the electron-accepting compound represented by the general formula (1) is appropriately referred to as “specific electron-accepting compound 1”
• the electron-accepting compound represented by the general formula (2) is appropriately referred to as “specific electron”. This will be referred to as “Receptive Compound 2”.
• the specific electron accepting compound 1 and the specific electron accepting compound 2 are collectively referred to as “specific electron accepting compound” as appropriate.
• R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, halogen atom, amino group, carboxy group, carbamoyl group, hydroxy group, alkylsulfonyl group, alkyl group. Or an aryl group, and two adjacent R 1 to R 4 may be bonded to form a ring.
• M represents an n-valent metal atom, and n represents an integer of 1 to 3.
• R 1 to R 10 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or Represents a phenylsulfonyl group, and at least one of R 1 to R 10 is a hydroxy group.
• X represents —S—, —SO 2 —, —SO 2 NH—, or —OCH 2 CH 2 O—.
• the specific electron accepting compound 1 is a compound represented by the general formula (1).
• R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, halogen atom, amino group, carboxy group, carbamoyl group, hydroxy group, alkylsulfonyl group, alkyl group. Or an aryl group, and the amino group, carbamoyl group, alkyl group, and aryl group may further have a substituent.
• the alkyl group represented by R 1 , R 2 , R 3 or R 4 in the general formula (1) preferably has 1 to 8 carbon atoms, and may be linear, branched or cyclic, You may have substituents, such as a phenyl group and a halogen atom.
• Examples of the alkyl group represented by R 1 , R 2 , R 3 or R 4 include methyl, ethyl, t-butyl, cyclohexyl and the like. More preferably, the alkyl group represented by R 1 , R 2 , R 3 or R 4 is linear or branched and has 1 to 4 carbon atoms (not including the carbon number of the substituent). .
• the aryl group represented by R 1 , R 2 , R 3 or R 4 is preferably a 3- to 6-membered ring having 3 to 6 carbon atoms and having a hetero atom. May be.
• Examples of the aryl group represented by R 1 , R 2 , R 3 or R 4 include phenyl, benzyl, tolyl, naphthyl, 2-furyl, 2-thienyl, 2-pyridyl and the like.
• the aryl group represented by R 1 , R 2 , R 3 or R 4 is more preferably a 5-membered or 6-membered aryl group having no heteroatoms and 6 to 8 carbon atoms. .
• Examples of the substituent that the amino group, carbamoyl group, alkyl group, and aryl group may have include a halogen atom, amino group, carboxy group, carbamoyl group, hydroxy group, alkylsulfonyl group, alkyl group, and aryl group.
• the number of carbon atoms of the substituent is preferably 1-8.
• R 1 to R 4 are preferably a hydrogen atom, an alkyl group, or an aryl group.
• R 1 is a hydrogen atom
• R 2 is a phenyl group or a C 2 or C 3 alkyl group (the carbon number of the phenyl group is 8 or 9)
• R 4 is an alkyl group having 2 or 3 carbon atoms having a phenyl group (8 or 9 carbon atoms including the carbon number of the phenyl group) is preferable.
• M represents an n-valent metal atom
• n represents an integer of 1 to 3.
• a sodium atom, a potassium atom, a copper atom, an aluminum atom, a calcium atom, a zinc atom etc. are mentioned, for example.
• a polyvalent metal atom that is, a divalent or higher metal atom is preferable
• M is preferably an aluminum atom, a calcium atom, or a zinc atom. More preferably, it is a zinc atom.
• the specific electron accepting compound 2 is a compound represented by the general formula (2).
• R 1 to R 10 are each independently a hydrogen atom, a halogen atom, a hydroxy group, a carboxy group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, or Represents a phenylsulfonyl group, and at least one of R 1 to R 10 is a hydroxy group.
• X represents —S—, —SO 2 —, —SO 2 NH—, or —OCH 2 CH 2 O—.
• the alkyl group and the alkoxy group represented by R 1 ⁇ R 10, an alkyl group represented by R 1 ⁇ R 10 are, but straight chain (e.g., n- butyl), branched (e.g. , Tert-butyl) or cyclic (eg, cyclobutyl).
• the alkoxy group represented by R 1 to R 10 preferably has 1 or 3 carbon atoms, and the alkyl group preferably has 1 or 4 carbon atoms.
• R 1 to R 10 are preferably a hydrogen atom, an alkyl group, a hydroxy group, a carboxy group, or an alkoxy group.
• Specific examples of the specific electron accepting compound 2 (compound (2-1) to compound (2-4)) are shown below, but the present invention is not limited thereto.
• the heat distribution display layer in the present invention needs to contain at least two of the specific electron accepting compound 1 and the specific electron accepting compound 2.
• the electron accepting compound contained in the heat distribution display is only one of the specific electron accepting compound 1 or the specific electron accepting compound 2, the raw storage stability of the heat distribution display is improved. I can't.
• the specific electron accepting compound 1 and the specific electron accepting compound 2 need to be contained in the heat distribution display layer in the present invention in a specific quantitative ratio. That is, when the specific electron-accepting compound 1 is A and the specific electron-accepting compound 2 is B, the quantity ratio (A: B) of both is 95: 5 to 50:50 on a mass basis.
• the quantity ratio (A: B) between the specific electron accepting compound 1 (A) and the specific electron accepting compound 2 (B) is preferably 95: 5 to 70:30 on a mass basis, and 90: More preferably, it is 10 to 80:20.
• the specific electron accepting compound 1 has a content ratio of 40% by mass or more in the all electron accepting compound. That is, all of the electron-accepting compounds composed of the specific electron-accepting compound 1, the specific electron-accepting compound 2, and other electron-accepting compounds that may be contained as necessary.
• the content of the specific electron accepting compound 1 is 40% by mass or more based on the mass.
• the heat distribution display layer in the present invention contains at least the specific electron accepting compound 2 in addition to the specific electron accepting compound 1. Therefore, it goes without saying that the content of the specific electron accepting compound 1 is less than 100% by mass with respect to the total mass of the total electron accepting compound.
• the heat distribution display layer in the present invention has the specific electron accepting compound 1 in a range in which the quantity ratio (A: B) of the both is 95: 5 to 50:50 on a mass basis. Containing.
• the upper limit of the content of the specific electron accepting compound 1 with respect to the total mass of the all electron accepting compound is preferably 95% by mass, and more preferably 90% by mass or less.
• the content of the specific electron accepting compound 1 with respect to the total mass of the all electron accepting compound is more preferably 50% by mass to 95% by mass, and particularly preferably 70% by mass to 90% by mass.
• the specific electron-accepting compound and other electron-accepting compounds are not included in the organic polymer composite.
• the content of the specific electron-accepting compound (total content of the specific electron-accepting compound 1 and the specific electron-accepting compound 2) is 20 with respect to the total solid content of the electron-donating dye precursor from the viewpoint of color density.
• the content is preferably from mass% to 1000 mass%, more preferably from 50 mass% to 500 mass%.
• the organic polymer composite in the present invention contains an electron donating dye precursor and a polymer.
• the form of the organic polymer composite is not particularly limited. Even if it is a form obtained by mixing at least an electron-donating dye precursor and a polymer, microcapsules (hereinafter simply referred to as “capsules”) produced using the polymer. It may be a form in which an electron-donating dye precursor is encapsulated.
• an electron-donating dye precursor as an organic polymer complex in the heat distribution display layer, it is possible to impart heat responsiveness that develops color by heat, as well as external heat energy such as heating and heating. It is possible to prevent the electron-donating dye precursor and the electron-accepting compound from reacting with each other before the treatment is performed, and to improve the storage stability of the heat distribution display.
• the electron donating dye precursor preferably used in the present invention is not particularly limited as long as it is substantially colorless, but it develops color by donating electrons or accepting protons such as acids.
• it has a partial skeleton such as lactone, lactam, sultone, spiropyran, ester, amide, etc., and when contacted with an electron-accepting compound, these partial skeletons are ring-opened or cleaved. What is a compound of these is preferable.
• Examples of the electron-donating dye precursor include triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leucooramine compounds, rhodamine lactam compounds, triphenylmethane compounds. Examples thereof include compounds, triazene compounds, spiropyran compounds, fluorene compounds, pyridine compounds, pyrazine compounds.
• phthalides are described in U.S. Reissue Patent No. 23024, U.S. Pat. Nos. 3,491,111, 3,491,112, 3,491,116, and 3,509,174.
• fluorans include U.S. Pat. Nos. 3,624,107, 3,627,787, 36,411, 3,462,828, 3,681,390, and 3,920,510. And compounds described in JP-A-3959571.
• spiropyrans include compounds described in US Pat. No. 3,971,808.
• pyridine-based and pyrazine-based compounds include compounds described in US Pat. Nos. 3,775,424, 3,853,869 and 4,246,318.
• fluorene compound include compounds described in JP-A No. 63-094878. Among these, black-colored 2-arylamino-3- [H, halogen, alkyl, or alkoxy-6-substituted aminofluorane] is particularly preferably used.
• 2-anilino-3-methyl-6-diethylaminofluorane 2-anilino-3-methyl-6-N-cyclohexyl-N-methylaminofluorane, 2-p-chloroanilino-3- Methyl-6-dibutylaminofluorane, 2-anilino-3-methyl-6-dioctylaminofluorane, 2-anilino-3-chloro-6-diethylaminofluorane, 2-anilino-3-methyl-6-N- Ethyl-N-isoamylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-dodecylaminofluorane, 2-anilino-3-methoxy-6-dibutylaminofluorane, 2-o-chloroanilino -6-dibutylaminofluorane, 2-p-chloroanilin
• the electron donating dye precursor is preferably used as an organic polymer composite encapsulated in a capsule made of a polymer described later from the viewpoint of storage stability and prevention of background fogging.
• the content of the electron donating dye precursor is 3% by mass to 30% by mass with respect to the total solid content of the heat distribution display layer from the viewpoint of color density, adhesion to the support, and prevention of adhesion to the heat source. It is preferably 5% by mass to 20% by mass.
• the organic polymer composite in the present invention contains a polymer.
• the polymer is not particularly limited as long as it is a polymer compound that can form an organic polymer complex together with the electron donating dye precursor described above, and polyethylene, polystyrene, polyvinyl, polyurethane, polyurea, polyurethane polyurea, or the like may be used. it can.
• the organic polymer composite in the present invention preferably contains a polymer obtained by using an isocyanate compound and a volatile organic solvent described later, and polyurethane polyurea. Is particularly preferred.
• the isocyanate compound for obtaining the polymer is not only an isocyanate compound having two or more isocyanate groups in an aromatic compound or hydrocarbon compound, but also a condensate, polymer or adduct using the isocyanate compound. including.
• a compound having two or more isocyanate groups in one molecule is preferred.
• Examples of compounds having two isocyanate groups in aromatic compounds and hydrocarbon compounds include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene- 1,4-diisocyanate, diphenylmethane-4,4′-diisocyanate, 3,3′-dimethoxy-biphenyl diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, xylylene-1,4-diisocyanate, xylylene- 1,3-diisocyanate, 4-chloroxylylene-1,3-diisocyanate, 2-methylxylylene-1,3-diisocyanate, 4,4'-diphenylpropane diisocyanate, 4,4'-diphenylhexaful Lopropane diisocyanate, trim
• bifunctional diisocyanate compound has been exemplified above, a trifunctional triisocyanate compound or a tetrafunctional tetraisocyanate compound inferred from these may be used.
• adducts of the above isocyanate compounds with bifunctional alcohols such as ethylene glycols and bisphenols and phenols can be used.
• condensates, polymers or adducts using isocyanate compounds include adducts of polyols such as burettes or isocyanurates and trimethylolpropane, which are trimers of the aforementioned bifunctional isocyanate compounds, and bifunctional isocyanate compounds.
• a formalin condensate of benzene isocyanate a polymer of an isocyanate compound having a polymerizable group such as methacryloyloxyethyl isocyanate, lysine triisocyanate, and the like can be used.
• xylene diisocyanate and its hydrogenated product, hexamethylene diisocyanate, tolylene diisocyanate and its hydrogenated product are used as the main raw materials, and these trimers (burette or isosinurate) as well as adducts with trimethylolpropane are multifunctional. These are preferred.
• the polyfunctional isocyanate is preferably an aromatic polyfunctional isocyanate, such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene-1,4-diisocyanate, xylylene-1
• Adducts of 1,3-diisocyanate, trimethylolpropane and xylylene-1,4-diisocyanate or xylylene-1,3-diisocyanate are preferred, and in particular, xylylene-1,4-diisocyanate and xylylene-1,3-diisocyanate, trimethylol.
• Adducts of propane and xylylene-1,4-diisocyanate or xylylene-1,3-diisocyanate are preferred.
• the volatile organic solvent means an organic solvent having a boiling point of 40 ° C. or higher and lower than 150 ° C., preferably an organic solvent having a boiling point of 40 ° C. to 130 ° C.
• Examples of the volatile organic solvent used to obtain the polymer include ethyl acetate (boiling point 77 ° C.), isopropyl acetate (boiling point 88 ° C.), butyl acetate (boiling point 124 to 127 ° C.), and isobutyl acetate (boiling point 118 ° C.).
• the organic polymer composite preferably has a volume average 50% particle size (D50v) of 0.1 ⁇ m to 5 ⁇ m.
• D50v volume average 50% particle size
• the particle size (volume average particle size) of the organic polymer composite is a value measured using a laser diffraction particle size distribution measuring device “LA750” manufactured by Horiba, Ltd.
• LA750 laser diffraction particle size distribution measuring device
• D50v volume average 50% particle size
• the volume average particle diameter (D50v) may be simply referred to as “volume average particle diameter” or “particle diameter”, and the same applies to the volume average particle diameter thereafter.
• the organic polymer composite may be obtained by dispersing an electron donating dye precursor-containing liquid containing the electron donating dye precursor, the isocyanate compound, and the volatile organic solvent in an aqueous phase, and It can be produced by preparing a dispersion liquid in which oil droplets containing a dye precursor-containing liquid are dispersed (dispersing step) and polymerizing the isocyanate compound in the oil droplets (polymerization step).
• the content of the volatile organic solvent in the dispersion is 10% by mass or less with respect to the content at the start of the polymerization reaction. Is preferred.
• the manufacturing method of an organic polymer composite is demonstrated in detail.
• the dispersion step in the present invention is a step of emulsifying and dispersing the electron-donating dye precursor-containing liquid (oil phase) in the water phase as oil droplets.
• Emulsification / dispersion can be easily carried out using means used for usual fine particle emulsification such as a high-speed stirrer and an ultrasonic dispersion device, for example, a homogenizer, a manton gorey, an ultrasonic dispersion device, a dissolver, a teddy mill and the like. Can be done.
• the mixing ratio of the oil phase to the water phase (oil phase mass / water phase mass) is preferably 0.5 to 1.5, more preferably 0.7 to 1.2. When the mixing ratio is in the range of 0.5 to 1.5, an appropriate viscosity can be maintained, the production suitability is excellent, and the stability of the emulsion is excellent.
• aqueous solution in which a water-soluble polymer is dissolved as a protective colloid for the aqueous phase to be used.
• the water-soluble polymer makes the dispersion uniform and easy, and stabilizes the emulsified and dispersed aqueous solution.
• the water-soluble polymer examples include polyvinyl alcohol and modified products thereof, polyacrylic acid amide and derivatives thereof, ethylene / vinyl acetate copolymer, styrene / maleic anhydride copolymer, ethylene / maleic anhydride copolymer, Mention may be made of isobutylene / maleic anhydride copolymer, polyvinylpyrrolidone, ethylene / acrylic acid copolymer, vinyl acetate / acrylic acid copolymer, carboxymethylcellulose, methylcellulose, casein, gelatin, starch derivatives, arabic gum and sodium alginate. Polyvinyl alcohol and modified products thereof, gelatin and modified products thereof, and cellulose derivatives are preferably used.
• water-soluble polymers are preferably those that do not react with isocyanate compounds or that are extremely difficult to react. For example, those having a reactive amino group in the molecular chain such as gelatin may be pre-removed. is necessary. Only one type of water-soluble polymer may be used, or two or more types may be used in combination.
• the polyether since the polyether also acts as a surfactant, when adding a polyether compound to the electron-donating dye precursor-containing liquid, it is possible to stably disperse without adding a surfactant separately.
• a surfactant may be added as necessary within a range that does not adversely affect the performance of the heat distribution indicator.
• the surfactant may be used by adding to either the oil phase or the aqueous phase.
• the amount of the surfactant used is preferably 1% by mass or less, particularly preferably 0.5% by mass or less, based on the mass of the oil phase.
• the surfactant used for emulsification and dispersion can be appropriately selected from anionic or nonionic surfactants.
• surfactants having a relatively long chain hydrophobic group are excellent.
• Surfactant Handbook "(Nishi Ichiro et al., Published by an industrial book (1980)).
• Preferred surfactants are alkali metal salts such as alkylsulfonic acid and alkylbenzenesulfonic acid, such as sodium alkylbenzenesulfonic acid, sodium alkylsulfate, dioctylsulfosuccinic acid sodium salt, polyalkylene glycol (for example, polyoxyethylene nonylphenyl). Ether), acetylene glycol and the like.
• compounds such as a formalin condensate of aromatic sulfonate and a formalin condensate of aromatic carboxylate, can also be used as a surfactant (emulsification aid). Specifically, it is a compound represented by the following general formula (I).
• the compounds represented by the following general formula (I) are described in JP-A-6-297856.
• R represents an alkyl group having a carbon number of 1 ⁇ 4
• X is SO 3 - or COO - represents
• M represents a sodium ion or potassium ion
• q is an integer of from 1 to 20 Represents.
• Alkyl glucoside compounds can also be used in the same manner. Specifically, it is a compound represented by the following general formula (II).
• R represents an alkyl group having 4 to 18 carbon atoms
• p represents an integer of 0 to 2.
• the surfactants may be used alone or in combination of two or more.
• the particle size of the emulsion particles which are oil droplets obtained by the dispersion step is preferably the same as the volume average 50% particle size (D50v) of the organic polymer composite described above, and the particle size of the emulsion particles is preferable. The range is the same.
• the polymerization step is a step in which an isocyanate compound contained in the oil droplet is subjected to a polymerization reaction.
• the content of the volatile organic solvent in the dispersion can be appropriately adjusted by adjusting the stirring speed and stirring time of the dispersion, the liquid temperature during the polymerization reaction, and the amount of exhaust air.
• the polymerization reaction can be carried out by adding a polymerization reaction catalyst of an isocyanate compound to the dispersion or increasing the temperature of the dispersion.
• a compound that causes an addition reaction with an isocyanate compound such as a polyol or a polyfunctional amino compound
• an isocyanate compound such as a polyol or a polyfunctional amino compound
• the isocyanate contained in the oil phase is only active hydrogen of water molecules. Instead, it reacts with the polyol and polyfunctional amino compound contained in the aqueous phase at the interface to form polyurethane and polyurea to form walls.
• Specific examples of the polyol that can be added to the aqueous phase include propylene glycol, glycerin, trimethylolpropane, and the like, and only one type may be used or two or more types may be used in combination.
• polyfunctional amino compound examples include diethylenetriamine, tetraethylenepentamine, and the like, and only one type may be used or two or more types may be used in combination. Furthermore, you may use a polyol and a polyfunctional amino compound together. These compounds are also described in the above “Polyurethane Resin Handbook”.
• the target organic polymer complex can be obtained by reacting for several hours.
• a metal-containing dye, a charge control agent such as nigrosine, or any other additive can be added as necessary. These additives can be added at the time of wall formation or at any time.
• the heating temperature for removing the volatile organic solvent depends on the kind of the volatile organic solvent used, but is preferably less than 100 ° C., more preferably 40 to 70 ° C.
• the content of the electron-donating dye precursor in the electron-donating dye precursor-containing liquid is preferably 5 to 50% by mass, and more preferably 10 to 30% by mass.
• the content of the isocyanate compound in the electron donating dye precursor-containing liquid is preferably 2 to 50% by mass, and more preferably 5 to 30% by mass.
• the content of the isocyanate compound in the electron donating dye precursor-containing liquid is preferably 5 to 75 parts by mass with respect to 100 parts by mass of the volatile organic solvent, and is preferably 10 to 50 parts by mass. Further preferred. When the content of the isocyanate compound is 5 to 75 parts by mass with respect to 100 parts by mass of the volatile organic solvent, the reactivity of the isocyanate compound can be easily controlled by controlling the evaporation of the volatile organic solvent.
• the content of the volatile organic solvent in the electron donating dye precursor-containing liquid is preferably 20 to 90% by mass, more preferably 30 to 70% by mass.
• the electron donating dye precursor-containing liquid may contain an ultraviolet absorber, an antioxidant, and the like as needed.
• the electron-donating dye precursor-containing liquid is prepared by mixing a predetermined amount of an electron-donating dye precursor, an isocyanate compound, a volatile organic solvent, and other components that are used as necessary, and a known method such as stirring or dispersion. It is prepared by using a technique.
• the electron donating dye precursor-containing liquid may be in the form of a solution or a dispersion.
• the heat distribution display layer in the present invention contains a binder.
• the binder include hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride salicylic acid copolymer, polyacrylic acid, polyacrylic acid Examples include amide, methylol-modified polyacrylamide, starch derivatives, casein, and gelatin.
• a water resistance improver can be added, or an emulsion of a hydrophobic polymer, specifically, an acrylic resin emulsion, a styrene-butadiene latex or the like can be added.
• the content of the binder is preferably 8% by mass to 30% by mass with respect to the total solid content of the heat distribution display layer, from the viewpoint of preventing transfer of the heat distribution display layer to the heat source, and 10% by mass to 20% by mass. % Is more preferable.
• polyvinyl alcohol is preferably used as the binder from the viewpoint of improving transparency, and modified PVA such as carboxy-modified polyvinyl alcohol and silica-modified polyvinyl alcohol can also be used.
• the heat distribution display layer may contain a known hardener or the like. Examples of the hardener include inorganic compounds such as boric acid, borax, and colloidal silica, aldehyde derivatives, and dialdehyde derivatives.
• the heat distribution display layer may further contain other components in addition to the essential components such as the specific electron accepting compound 1, the specific electron accepting compound 2, and the binder.
• the other components are not particularly limited and can be appropriately selected according to the purpose or necessity.
• the heat distribution display layer may contain a sensitizer in order to promote color development.
• a sensitizer a low-melting-point organic compound having moderately aromatic groups and polar groups in the molecule is preferable.
• benzyl p-benzyloxybenzoate ⁇ -naphthylbenzyl ether, ⁇ -naphthylbenzyl ether, ⁇ -naphthoic acid phenyl ester, ⁇ -hydroxy- ⁇ -naphthoic acid phenyl ester, ⁇ -naphthol- (p -Chlorobenzyl) ether, 1,4-butanediol phenyl ether, 1,4-butanediol-p-methylphenyl ether, 1,4-butanediol-p-ethylphenyl ether, 1,4-butanediol-m- Methyl phenyl ether, 1-phenoxy-2- (p-tolyloxy) ethane, 1-phenoxy-2- (p-ethylphenoxy) ethane, 1-phenoxy-2- (p-chlorophenoxy) ethane
• the heat distribution display layer may contain a pigment.
• a pigment used in the heat distribution display layer, either an organic pigment or an inorganic pigment can be used.
• the volume average particle size of the pigment used in the heat distribution display layer is preferably 0.10 to 5.0 ⁇ m.
• the type of pigment that can be used in the heat distribution display layer is not particularly limited, and can be appropriately selected from known organic and inorganic pigments.
• Inorganic pigments such as titanium, kaolin, aluminum hydroxide, amorphous silica, and zinc oxide, and organic pigments such as urea formalin resin and epoxy resin are preferable. Of these, kaolin, aluminum hydroxide, and amorphous silica are particularly preferable. These pigments may be used alone or in combination of two or more.
• a pigment whose surface is coated with at least one selected from the group consisting of higher fatty acids, higher fatty acid metal salts, and higher alcohols can be suitably used. Examples of the higher fatty acid used for the surface treatment (surface coating) include stearic acid, palmitic acid, myristic acid, lauric acid, and the like.
• the pigment may be, for example, sodium metametaphosphate, partially or fully saponified polyvinyl alcohol, modified polyvinyl alcohol, polyacrylic acid copolymer, various surfactants, and the like, preferably partially or fully saponified polyvinyl.
• itaconic acid-modified polyvinyl alcohol, terminal alkyl-modified polyvinyl alcohol, polyacrylic acid copolymer ammonium salt dispersed to the volume average particle size with a known disperser such as a dissolver, sand mill, or ball mill. It is preferred that That is, the pigment is preferably used after being finely dispersed until the 50% volume average particle size of the pigment reaches a particle size in the range of 0.1 to 5.0 ⁇ m.
• the heat distribution display layer may contain a lubricant, a release agent, or a slip agent.
• Lubricants, mold release agents and slip agents (hereinafter sometimes referred to as “lubricants etc.”) used in the heat distribution display layer are usually liquids at room temperature or have a melting point of less than 40 ° C. and a melting point. A form containing a lubricant at 40 ° C. or higher is preferable.
• silicone oil examples include silicone oil, liquid paraffin, and lanolin, and silicone oil is particularly preferable.
• silicone oils may have a substituent such as a carboxyl group or a polyoxyethylene group, and the viscosity of the silicone oil is preferably 100 cps to 100,000 cps.
• Examples of the lubricant having a melting point of less than 40 ° C. include polyoxyethylene alkyl ether, polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether phosphate and the like.
• the above-mentioned lubricants that are liquid at normal temperature and lubricants having a melting point of 40 ° C. or less may be used alone or in combination of two or more.
• a melting point of 40 ° C. or higher a melting point of 160 ° C. or lower, preferably 140 ° C. or lower is desirable, stearic acid amide (melting point 100 ° C.), methylol stearic acid amide (101 ° C.), Polyethylene wax (melting point 110 ° C.
• paraffin wax with melting point 50-90 ° C. glycerin tri-12-hydroxystearate (melting point 88 ° C.), oleic acid amide (melting point 73 ° C.), zinc oleate (melting point 75 ° C.), Lauric acid amide (melting point 84 ° C.), aluminum stearate (melting point 102 ° C.), manganese stearate (melting point 112 ° C.), zinc stearate (melting point 125 ° C.), calcium stearate (melting point 160 ° C.), ethylene bisstearamide ( Melting point 140 ° C), magnesium stearate (melting point 132 ° C), PAL Chinsan magnesium (melting point 122 ° C.), magnesium myristate (melting point 131 ° C.), and the like.
• These lubricants having a melting point of 40 ° C. or higher may be used alone or in combination of two or more.
• the lubricant used in the present invention is insoluble in water, it is added to the heat distribution display layer in the form of dispersion or emulsion.
• aqueous dispersion dispersed with a known disperser such as a homogenizer, dissolver or sand mill in the presence of a water-soluble polymer such as polyvinyl alcohol or a dispersant such as various surfactants.
• a preferable volume average particle size of the dispersed lubricant or the like dispersed in the lubricant is 0.1 ⁇ m to 5.0 ⁇ m, and more preferably 0.1 ⁇ m to 2.0 ⁇ m.
• water-soluble lubricants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl ether acetate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether phosphate, etc. are optional in consideration of solubility. And can be added to the heat distribution display layer.
• the heat distribution display layer may contain a matting agent.
• a matting agent for example, fine particles such as starch obtained from barley, wheat, corn, rice, beans, cellulose fiber, polystyrene resin, epoxy resin, polyurethane resin, urea formalin resin, poly (meth) acrylate resin, polymethyl (Meth) acrylate resin, copolymer resin such as vinyl chloride or vinyl acetate, fine particles of synthetic polymer such as polyolefin, inorganic substances such as calcium carbonate, titanium oxide, kaolin, smectite clay, aluminum hydroxide, silica, zinc oxide Examples thereof include fine particles.
• the matting agent is preferably a particulate material having a refractive index of 1.45 to 1.75, and the volume average particle diameter is 1 ⁇ m to 20 ⁇ m ( In particular, 1 ⁇ m to 10 ⁇ m) is preferable.
• a surfactant to the coating solution for forming the heat distribution display layer in order to form the heat distribution display layer uniformly on the support.
• a surfactant sulfosuccinic acid-based alkali metal salts, fluorine-containing surfactants and the like are preferable. Specific examples include di- (2-ethylhexyl) sulfosuccinic acid and di- (n-hexyl) sulfosuccinic acid.
• Examples include sodium salts, potassium salts, or ammonium salts, acetylene glycol derivatives, sodium perfluoroalkyl sulfate, potassium salts, ammonium salts, perfluoroalkyl betaine compounds, and the like.
• the heat-fusible substance can be contained in the heat distribution display layer for the purpose of improving the heat response.
• heat fusible substances include aromatic ethers, thioethers, esters, aliphatic amides, ureidos, and the like. Examples of these are disclosed in JP-A Nos. 58-57989, 58-87094, 61-58789, 62-109682, 62-132673, 63-151478, and 63-235961. It is described in Japanese Laid-Open Patent Publication Nos. 2-18489 and 2-215585.
• UV absorber examples include benzophenone UV absorbers, benzotriazole UV absorbers, salicylic acid UV absorbers, cyanoacrylate UV absorbers, and oxalic acid anilide UV absorbers.
• examples thereof include JP-A-47-10537, 58-111942, 58-212844, 59-19945, 59-46646, 59-109555, 63-53544, Japanese Patent Publication Nos. 36-10466, 42-26187, 48-30492, 48-31255, 48-41572, 48-54965, and 50-10726, U.S. Pat. 3707375, 3754919, and 4220711.
• antioxidants include hindered amine antioxidants, hindered phenol antioxidants, aniline antioxidants, and quinoline antioxidants. Examples of these are described in JP-A Nos. 59-155090, 60-107383, 60-107384, 61-137770, 61-139481, 61-160287, and the like. Yes.
• antistatic agent include metal oxide fine particles, inorganic electrolytes, and polymer electrolytes.
• the temperature [° C.] at which the color density reaches the background density (Dmin) +0.1 is TA
• the temperature [° C.] at which the color density reaches the maximum density (Dmax) ⁇ 0.1 is TB
• the intermediate temperature [° C.] between the TA and the TB is TC, it is preferable to satisfy the following formulas (1) and (2).
• DA represents the optical density of the color-developing portion that has developed color by heating the heat distribution display layer to the temperature TA
• DB represents the heat distribution display layer heated to the temperature TB.
• the color density represents the optical density of the developed color part
• DC represents the optical density of the color developed part that developed color by heating the heat distribution display layer to the temperature TC.
• the fraction shown in the equation (1) is also called ⁇ 1
• the fraction shown in the equation (2) is also called ⁇ 2.
• the background density (Dmin) is the surface of the heat distribution display layer where no image is recorded before the heat distribution display layer is subjected to heat energy application processing such as heating or heating (uncolored portion) ) Optical density.
• a Macbeth densitometer (RD-19I, manufactured by Macbeth Co., Ltd.) was brought into contact with a heat source heated to an arbitrary temperature for 10 seconds at a pressure of 500 g / cm 2 using a 10-series thermal property tester (manufactured by Shinto Kagaku Co., Ltd.). ), The temperature at which the optical density becomes the optical density of the non-colored portion +0.1 is defined as the static color development start temperature, and this is TA.
• the temperature [° C.] reaching the concentration obtained by adding 0.1 to the background density (Dmin) is TA, and the concentration obtained by adding 0.1 to the background density (Dmin), that is, the heat distribution display layer is set to the temperature TA.
• Dmin the concentration obtained by adding 0.1 to the background density (Dmin)
• DA the optical density of the colored part, which is the colored part when heated.
• the maximum density (Dmax) refers to the maximum optical density of the color-development portion that is colored by applying heat energy from the outside such as heating or heating to the heat distribution display layer.
• the temperature [° C.] reaching the concentration obtained by subtracting 0.1 from the maximum concentration (Dmax) is TB, and the concentration obtained by subtracting 0.1 from the maximum concentration (Dmax), that is, the heat distribution display layer is set to the temperature TB.
• DB be the optical density of the color-developing part, which is the part colored by heating.
• the temperature [° C.] between TA and TB is TC
• the optical density of the color-development portion that is colored by heating the heat distribution display layer to the temperature TC is DC.
• the optical density of the color-developing portion that has developed color by applying heat energy from the outside is also referred to as color density.
• the color density (optical density) of the color development portion that develops color by heating to a small temperature difference By changing the color density (optical density) of the color development portion that develops color by heating to a small temperature difference, a difference in color density according to the temperature difference can be obtained over a wide temperature range. Therefore, even if the temperature difference of each part of the measurement target surface where the heat distribution is to be confirmed is large, an image with gradation can be obtained and the heat distribution can be easily confirmed. As described above, since the color density (optical density) changes small with respect to a small temperature difference, it is preferable that the expressions (1) and (2) are satisfied.
• ⁇ 1 and ⁇ 2 are 0.011 or more, the color density difference is not too small, and the heat distribution can be confirmed. If ⁇ 1 and ⁇ 2 are 0.035 or less, the color density difference is not too large, and the temperature range in which gradation can be expressed is not too narrow, which is practical. Moreover, it is preferable that the TA, the TB, the TC, the DA, the DB, and the DC satisfy the following formula (4).
• the difference between ⁇ 1 and ⁇ 2 is preferably within ⁇ 0.016.
• the difference between ⁇ 1 and ⁇ 2 is within ⁇ 0.016, the color gradation is closer to a straight line, and the temperature distribution can be easily discriminated intuitively.
• the difference between ⁇ 1 and ⁇ 2 is more preferably within ⁇ 0.01 from the viewpoint of ease of consistency with visual evaluation.
• the ⁇ 1 is preferably 0.015 ⁇ ⁇ 1 ⁇ 0.03, more preferably 0.018 ⁇ ⁇ 1 ⁇ 0.027 from the viewpoint of the temperature distribution measurable range.
• the ⁇ 2 is preferably 0.015 ⁇ ⁇ 2 ⁇ 0.03 and more preferably 0.018 ⁇ ⁇ 2 ⁇ 0.027 from the viewpoint of the temperature distribution measurable range.
• the temperature difference between the TA and the TB (TB ⁇ TA) is preferably 30 ° C. or more. Further, TB-TA is preferably 30 ° C. to 75 ° C. Furthermore, from the point of the temperature measurement range, it is preferable that the TA, the TB, the DA, and the DB satisfy the following formula (3).
• the fraction represented by the formula (3) is also referred to as ⁇ 3.
• ⁇ 3 is 0.011 or more, the temperature measurement range is not too wide and suitable for confirming the distribution, and if it is 0.029 or less, the temperature distribution measurement range is not too narrow. It is.
• the ⁇ 3 is preferably 0.013 ⁇ ⁇ 3 ⁇ 0.027, and more preferably 0.015 ⁇ ⁇ 3 ⁇ 0.025 from the viewpoint of the temperature distribution confirmation range.
• the heat distribution display layer in the present invention is an application for forming a heat distribution display layer obtained by blending an organic polymer composite, an electron-accepting compound, a binder, and the optional component that can be contained in the heat distribution display layer. It can be formed by applying a liquid on a support.
• an electron-accepting compound is added to the coating liquid for forming the heat distribution display layer, and further a thermal sensitizer is added, it is added separately by emulsification dispersion, solid dispersion, or atomization, or After mixing appropriately, it can be added after being emulsified, dispersed, or atomized.
• Examples of the emulsifying and dispersing method include a method of dissolving these compounds in an organic solvent and adding the water-soluble polymer aqueous solution while stirring with a homogenizer or the like. In promoting the formation of fine particles, it is preferable to use one or more of a hydrophobic organic solvent, a surfactant, and a water-soluble polymer.
• these powders can be put into a water-soluble polymer aqueous solution to be finely divided using a known dispersing means such as a ball mill.
• the microparticulation is preferably performed so as to obtain a particle size that can satisfy the characteristics required for the heat distribution display and its manufacturing method such as thermal sensitivity, storage stability, transparency of the recording layer, and manufacturing suitability.
• the electron-accepting compound is preferably prepared so that it is not in an emulsified state but in a solid-dispersed state.
• the coating liquid for forming the heat distribution display layer can be prepared, for example, by mixing the organic polymer composite produced as described above and a solid dispersion containing an electron accepting compound.
• the water-soluble polymer used as the protective colloid in the preparation of the organic polymer composite and the water-soluble polymer used as the protective colloid in the preparation of the dispersion function as a binder in the heat distribution display layer. . It is also a preferred embodiment to prepare a coating solution for forming a heat distribution display layer by adding and mixing a binder separately from these protective colloids.
• the heat distribution display layer in the present invention is preferably provided in the range of 1 to 25 g / m 2 on the support.
• the thickness of the heat distribution display layer is preferably 1 to 25 ⁇ m.
• two or more heat distribution display layers can be laminated and used. In this case, the total amount of the heat distribution display layer in the heat distribution display body is 1 to 25 g / m 2. Is preferred.
• the support in the present invention can be appropriately selected from known supports.
• Cellulose derivative films such as cellulose film, polyolefin films such as polystyrene film, polypropylene film and polyethylene film, poly-4-methyl-1-pentene, ionomer, polyvinyl chloride, polyvinylidene chloride, ABS resin, AS resin, methacrylic resin, Polyvinyl alcohol, EVA, epoxy resin, unsaturated polyester resin, phenol resin, urea / melamine resin, polyurethane resin, silicone resin, polyamide resin, polyacetal, polycarbonate, modified polyphenylene agent Polyester resin, fluororesin, polyphenylene sulfide, polysulfone, polyarylate, polyetherimide, polyethersulfone, polyetherketone, polyamideimide, polyallyl ether nitrile
• the thermal contraction rate in the longitudinal and lateral directions of the support is preferably less than 1%, and more preferably 0.5% or less.
• a support made of a polymer film is preferable, and a synthetic film such as a polyester film such as polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate, a cellulose triacetate film, or a polyolefin film such as polypropylene or polyethylene is used. Examples thereof include molecular films, and a polyethylene terephthalate (PET) or polyimide support is particularly preferable.
• the thickness of the synthetic polymer film is preferably 20 ⁇ m or more, more preferably 30 ⁇ m or more, and further preferably 50 ⁇ m or more. When the thickness of the synthetic polymer film is 10 ⁇ m or more, it is easy to handle without wrinkles.
• the synthetic polymer film may be colored in an arbitrary hue.
• a method for coloring the synthetic polymer film a method of forming a film by kneading a dye into a resin before forming the resin film, a coating solution in which the dye is dissolved in an appropriate solvent, and preparing this as a colorless transparent
• a known coating method such as a gravure coating method, a roller coating method, a wire coating method, or the like may be used on such a resin film.
• it is preferable that polyimide is formed into a film and subjected to heat treatment, stretching treatment, antistatic treatment or the like.
• a polyimide film having a thickness of 50 ⁇ m or more is particularly preferable.
• the heat distribution display of the present invention may have other layers such as a protective layer, an intermediate layer and a back layer in addition to the heat distribution display layer as long as the effects of the present invention are not impaired.
• a coating liquid for forming a heat distribution display layer (hereinafter, referred to as “coating liquid for forming a heat distribution display layer”) is applied to one side of a support to distribute heat. It can be manufactured by forming a display layer. Further, if necessary, an intermediate layer coating solution and a protective layer coating solution are applied onto the heat distribution display layer, and with or without the application, on the opposite side to the side as described above. Further, a back layer composed of a single layer or a plurality of layers can be formed by applying a back layer coating solution. Furthermore, you may form another layer in said one and the other as needed.
• the heat distribution display layer, the intermediate layer, and the protective layer may be formed at the same time.
• the heat distribution display layer forming coating solution, the intermediate layer coating solution, and the protective layer coating solution are supported. It can be formed by applying multiple layers simultaneously on the body.
• the temperature distribution confirmation method of the present invention uses the heat distribution display of the present invention described above.
• the heat distribution display body of the present invention is disposed on a heating surface such as a heating roller or a hot plate, and the heat distribution display layer of the heat distribution display body of the present invention is heated by the heat of the heating surface.
• a heating surface such as a heating roller or a hot plate
• an image is recorded on the heat distribution display to confirm the heat distribution.
• the heat distribution display of the present invention may be arranged so as to be in direct contact with the heating surface, or an intermediate body such as a sheet or film is sandwiched between the heating surface and the heat distribution display of the present invention. You may arrange.
• Example 1 [Manufacture of organic polymer composites]
• an electron donating dye precursor 54.6 parts of a compound represented by the following structural formula [201] and 2.08 parts of a compound represented by the following structural formula [207] were added to 107 parts of ethyl acetate, After heating to 70 ° C. and dissolution, it was cooled to 45 ° C. To this, 87.3 parts of isocyanate (“Takenate D127N” (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) was added and mixed to obtain a solution.
• isocyanate (“Takenate D127N” (trade name) manufactured by Mitsui Takeda Chemical Co., Ltd.) was added and mixed to obtain a solution.
• This solution was added to an aqueous phase consisting of 276 parts of a 5.9% aqueous polyvinyl alcohol solution (“MP-103” (trade name) manufactured by Kuraray Co., Ltd.), and then Robotics (manufactured by Tokushu Kika Co., Ltd.) was added. Emulsification was carried out at a rotational speed of 6800 rpm to obtain an emulsion. After adding 23 parts of water and 5.7 parts of tetraethylenepentamine to the obtained emulsion, an encapsulation reaction was performed at a temperature of 60 ° C. for 4 hours, and finally the concentration was adjusted to 22% with water. A polymer composite liquid A containing particles having an average particle diameter of 4.8 ⁇ m was obtained.
• the compound (1-1) [specific electron accepting compound 1] and the compound (2-1) [specific electron accepting compound 2] used for the preparation of the electron accepting compound dispersion B are represented by the following structural formula. .
• pigment dispersion C 180 parts of distilled water, 110 parts of calcium carbonate, 3 parts of sodium hexametaphosphate 40% aqueous solution (sodium hexametaphosphate, manufactured by Koizumi Chemical Co., Ltd.), 40% aqueous solution of acrylic acid / maleic acid copolymer soda salt (Kao Soap Co., Ltd.) ) “Poise 520”)) 1.5 parts added, dispersed with a sand grinder, and a calcium carbonate dispersion (pigment dispersion C) containing particles having a median particle size of 1.0 ⁇ m (measured with “LA750” manufactured by HORIBA, Ltd.) Got.
• An undercoat layer is formed by applying the coating liquid D for the support undercoat layer to a high-quality paper having a smoothness of 150 seconds according to JIS-8119 so that the coating amount after drying is 8 g / m 2 by a blade coater. This was used as a support.
• the heat distribution display body 1 was used as the heat distribution display body of Example 1.
• Example 2 to Example 7 and Comparative Example 1 to Comparative Example were the same except that the electron-accepting compound used in the production of the heat distribution display 1 of Example 1 was changed as shown in Table 1 below. 6 heat distribution displays were produced.
• the structures of the compound (3) used in Comparative Example 4 and the compound (4) used in Comparative Example 6 are as follows, and the compounds 2-2 to 2-4 are represented by the above exemplified compounds (2 -2) to (2-4).
• ⁇ 1 and ⁇ 2 are 0.015 to 0.03, and their difference (
• D Outside the above range
• the heat distribution display of the example can display heat distribution even with a large temperature difference and is excellent in the raw preservation of the heat distribution display.
• the entire surface of the heat distribution display layer was darkly colored, and an image without distinction of shading was recorded, and the heat distribution could not be displayed.
• the raw storage stability is not excellent.

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